Modified acrylate polymers and compositions containing the same



United Saws, ,Patdi MODIFIED ACRYLATE POLYMERS 'CQM- t' POSITIONS CONTAINING TI -IE SAME Norman G. Gaylord,'Westbury, N. Y., assignor to Interchemical Corporation, New York, N. Y., a corporation of Ohio No Drawing. Application May 28, 1956 1 Serial No. 587,492

6 Claims. (Cl. zen-45.2

This invention relates'to new polymeric materials and to coating compositions containing these new polymers. More particularly the invention relates to new addition type polymerization products that are compatible with organic solvent soluble thermosetting urea-formaldehyde and melamine-formaldehyde resins and reactive with these thermosetting aminoplast resins -to form homogeneous clear films.

The new resins are copolymers of glycerol oE-monoallyl ether, methacrylic acid or acrylic acid and at least one ester of acrylic or methacrylic acid with an aliphatic monohydric alcohol having 1 to 8 carbon atoms. Preferably the copolymers contain both an acrylic acid ester and methacrylic acid ester. The new-resins contain 5 to 30 parts of glycerol m-mono-allyl ether and "5 to 15 parts of methacrylic acid or acrylic acid for each 100 parts of acrylate type ester. In the preferred resins the acrylate type ester will consist of 25 to 75% acrylate ester and 75 to 25% methacrylate ester, especially methyl methacrylate. Minor amounts of other copolymerizable monomers may be included in making the resins provided these other monomers do not constitute more than about 20% of the total reactants. Typical additional reactants include: acrylonitrile, bis ethylene glycol maleate, dimethyl maleate, dimethyl fumarate, and vinyl butyl ether; I p

The new coating compositions of the present invention comprise coating compositions whose resinous film forming component comprises organic solvent soluble heat reactive aminoplast resin and the new copolymers defined hereinabove.

In the preparation of the new copolymers of the present invention I may use, as the acrylic acid ester, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethyl hexyl acrylate or, in general, acrylic acid esters of alcohols containing 1 to 8 carbon atoms.

methacrylate, butyl methacrylate, 2-ethyl hexyl methacrylate or, in general, anymethacrylic acid ester of an alcohol containing 1 to 8 carbon atoms. I The glycerol mono-allyl ether used as one of the monomers in making the new copolymers has recently began a commercial product. It is readily prepared by reacting allyl chloride with the mono-sodium derivative of glycerol. I

The new copolymers made in accordance-with the present invention can be represented as containing the following structural units:

(A) -CHr-CH- Similarly, ,for the methacrylic acid ester, I may use methyl .methacrylate, ethyl fromjthe acrylate type ester, where R is H or CH; and Ris an alkyl group containing 1- to 8 carbonatoms.

It will be understood that the new copolymers do not contain the structural groupings A, B and C in equal amounts but, as indicated hereinabove, in the ratio of 5'to:30 :parts of A and 5 to 15 parts of B for each 100 parts of =C.' The acrylate ester type unit being the most prevalent, the copolymer could be generally described as a modified acrylate type of polymer.

The new'polymers are made in conventional manner, for example; by mixing all of the reactants in a volatile solvent and heating with a free radical forming catalyst.

proved copolymers of the present invention.

Substantiallyv 100% conversion of the monomers to soluble polymer is obtained. 1

The following examples will further illustrate the Example 1 200 grams of n-butyl acrylate dissolved in 100 grams of xylene wasadded dropwise over a period of four hours toa solutionof 4 grams of benzoyl peroxide in 100 grams of xylene while maintainingthe temperature;

at C. At the end of 12 hours, the temperature was raised to the reflux point in order to destroy excess catalyst. A sample heated to 150 C. for 30 minutes to remove volatile components indicated conversion of monomer to polymer. 1

Example 2 50 grams of glycerol a-allyl ether (0.38 mole) was dissolved in 130 grams of xylene and placed in a 1 liter flask. A mixture of 8,0 grams of methyl methacrylate (0.87 mole), grams of butyl acrylate (0.94 mole),

10 grams of acrylic acid (0.14 mole) and 5.2 grams of benzoyl peroxide was dissolved in grams of xylene and placed in a dropping funnel and added dropwise to I the solution of glycerol allyl etherover a period of four hours while maintaining the temperature at 80 C. The reaction mixture was maintained at 80. C. for an additional 15 hours after the dropwise addition was completed. Then the temperature was raised to reflux and 7 held there for 30 minutes to destroy excess catalyst. Re-

. pressure followed by another 30 minutes at C.'at.5 l

moval of volatilecomponents from a sample of the product indicated 96% conversion of monomers to polymer.

Volatile components were removed by heating a sample of the resin at 150 C. for 30 minutes at atmospheric of mercury pressure.

The resins of Examples land 2 were compared by blending each of them in solution with the same quantity and type of organic solvent soluble thermosetting melamine form-aldehyde resin. Films of each solution were cast on steel panels andbaked at 177 c. for 30 minutes. The, baked film made from the solution contain-..

ing theresin fof Example 2 was a clear, cured film, having good flexibility and good surface hardness, while the made from the solution containing the resin from sept. 23, 19 5...

int-- Example" 1' was hazy and had poor surface hardness indici fi il g'ifib difi ifi'fibilityfld nOIi-Elirifigi Example 3 50 grams of glycerol a-allyl ether'vva's dissolvedin 120' grams of xylene and placed in a 1-liter fiask. A mixture of 100 grams of methyl methacrylate, 100 grams of ethyl hexyl acrylate, 10 grams of methacrylic acid and 4.8 grams of azo-di-isobuty'ronitrile was dissolved in 120 rams: ee" xylene i and added dropwi'se over a period of four hours to the solution of glycerol a-allyl ether. The

temperature of the reaction mixture were maintained at The" reacti n mixture at this 'peinteentained- 50%" nonvolatiles, indicating 100% conversion'of 'm'onomersto' polymers.

Examp'le'4 40 grams of glycerol a-allylether was dissolved in 120 grams of xylene and placed ina--1 liter flask. A

mixture of 70 grams of methyl methacrylate; 130 gramsof n-butyl acrylate and 4.8" grams of-benzoyl-peroxide dissolved in 120 grams of xylene -was' addeddropwise over a-periodof four hours. The temperature'wasmaintained' at 80 C.- during the additionand for an additional8 hoursafter the'additio'n'was complete. Arr-additional 2.4 grams of benzoyl peroxide was added-and-the mixture was heated at 80 C.fo1'-'six hours and then refluxed for 30 minutes. Adeterminat'ion of: non-volatiles content indicated 97% conversion of monomers to polymers.

v Example-5 30g'rams 'of"glycerol a-allyl etherwasdissolve'd' in 120 grams'of xylene. A mixture of 120' grams of methyl methacrylate, 80 grams ofZ-ethylbfltyl acrylate, '10 grarns of methacrylic' acid and 4.8 grams of azo diisobutyronitrile, dissolved in 120 grams of'xylene, is added dropwise,- dur'ing a period of four'hou'rs, to the glycerol or-allyl ether'soluti'on maintained at 80 Cithrou-gh'oitt theaddi; tion and for an additional seven'ho'ursafte'r the addition was complete. Then '-an additional 2.4 grams of azodiisobutyronitrile is added and heating at 80 C. is continued for an additional six hours. The-temperature isth'en raised to 140 C. for one-half hour to destroy excess catalyst. The resulting solution contained 50% non volatil'es indicating 100% conversion 0f monomers =to polymers.

Example- 6 A mixtureof 90"grams methyl methacrylate, 110' grams of ethylbutyl acrylate, 10 grams of'methacrylic'acid and 4.8 grams of azo-diisobutyroriitrile, dissolved'in 120 grains of xylene is'added dropwise to a well stirred"soluti on of 30"gra'ms of glycerol-allyl ether maintained at 80 The addition'requires about'4 hours and heating at' 80 C. 'is continued for'an additional 8 hours. A determina -Examp'le 7 A mixture of 80 grams of methyl methacrylate; grams of butyl acrylate, '10 grams of rnethac"rylic" acid tion requires about 4 hours and the temperature is maintained at"'80' C. for hours after the addition is complete. A non-volatile determination on the resulting solution indicated 98% conversion of monomers to polymers.

The novel compositions of the present invention contain the novel resins described and illustrated hereina bove -and an organic solvent soluble thermosetting 1 aminoplastyre'sin, such as the urea-aldehyde resins, the

melamine-aldehyde resins, the dicyandiamide-aldehyde resins; e'tc. Thealdehyde most" generally 'used'is" formaldehyde but other'aldehydes, such'as acetaldehydeaci'olein, and the like can be used. The aminoplast resins are readily -available commercial products 'und'er such tradenames as Resimene,-Ufor-mite'- and Melmac.

Volatile solvents that-can-be used in formulating the coating compositions of "the present invention include such solvents as aromatic hydrocarbons such as benzene,

,- toluene, xylene; esters" such' as butyl acetate, amyl nice tate, dibutyl phthalate, 'ethers,1espe'cially-ethers' of glycols or dig'lycols.

-A distinct advantage$ of thecompositions ofthe present-invention is that-they can be cured to-insoluble 'filin l without=-the-use of catalysts. Conventional catalysts for and 4.6 "grams of benzoyl peroxide dissolved 'in 11 5 grams of xylene is added drop'wise to' a well' stirred solution of'20 grams-"of glycerol a-allylieth'er dissolved-in 115 grams ofx'ylene'maintained'at' C. Tl1e"a"ddicuring aminop'last resin can be used but sincethecatalyst is unnecessary it is preferred that itbe omitted.

The-rollowlng' example in which the 'parts are by weight illustrate coating compositions made-inaccordan'ce Wlth the mvention. The --'ex'pression -Bonderite steel-' as employed in this-example and as understood-in the -trade refers-to a lbw-carbonsheet steel which" has been treated='by'-the" proprietary Bonderite process of the Parker-'Rustproof Company, Detroit, Michigan.- Steel coated with f-Bon'derit- 100 has" athin adherent coating of chromium, iron, 1 and zinc phosphates, which coating inhibits-corrosionand'greatly-improves adhesion of paints, primers, enamels; and the like to the steel.

Example 8 A white-enamelfor-use as an-appliance finish is prepared by-blending '40 parts titanium dioxide, 24 parts of organic solvent soluble thermosetting melamine-formaldehyde resinand 72 parts Ma 49% solution of the resin of Example 7 in xylol and enough volatile solvent to g'ive sprayahle composition. The enamel was sprayed-on primed'and unprimed Bonderite 100- steel and cured by baking at 350 F. for 30 minutes to give tough glossy fiIi'nshai/in'g'good soap and detergent resistance.

simnar enamels can be made by substituting other resins comprising copolymers of glycerol et-allyl ether, acrylic orme'tha'cr'ylic-acid and an acrylate or methacrylate ester as described herinabove. The ratio of thermosetting resin to copolymerresin is preferably within the range of disclosed inthe above examples we have, for instance made good enamels" from each'of the copolymerre's'in's prepared from" the followingspecific types and amounts of monomers.

. Parts (A)'Glycerol a allyl ether l5 Methyl methacrylate 40 Butyl acrylate 60 Methacrylic acid 5 (B)' Glyc'e rol a-allyl 'ether e s 20 Butyl acrylate 60 I Methacrylic acid -s 5 (C) Glycerol a-allyl ethers a 25 Methyl methacrylate 40 Butyl acrylate 60 Methacrylic acid 5 (D) Glycerol a-allyl ether; 20 Methyl methacrylate 40 Butyl acrylate 60 Methacrylic acid.. t0

Iclaim:

1. Novel resins comprising the addition polymeriza tion products of (a) 5 to 30 parts of glycerol u-monoallyl ether, (b) 5 to 15 parts of an acrylic monomer of the group consisting of acrylic acid and methacrylic acid, and (c) 100 parts of an acrylic type ester having the formula H2=('3- o- 0-R' where R represents a member of the group consisting of H and CH and R is an alkyl group containing 1 to 8 carbon atoms.

2. Novel resins comprising the addition polymerization products of (a) 5 to 30 parts of glycerol a-mono-allyl ether, (b) 5 to 15 parts of methacrylic acid, and (c) 100 parts of a mixture consisting of 25 to 75% of an acrylic ester having the formula where R is an alkyl group containing 1 to 8 carbon atoms and 75 to 25 of an acrylic ester having the formula CHz=CC-OR' where R is an alkyl group containing 1 to 8 carbon atoms.

3. Novel resins comprising the addition polymerization products of (a) 5 to 30 parts of glycerol u-mono-allyl ether, (b) 5 to 15 parts of methacrylic acid, and (c) 100 parts of a mixture consisting of 25 to 75% of Butyl acrylate and 75 to 25% of methyl methacrylate.

4. The method of preparing resins which includes heating (a) 5 to 30 parts of glycerol a-mono-allyl ether, (b) 5 to 15 parts of an acrylic monomer of the group consisting of acrylic acid and methacrylic acid, and (3) 100 parts of acrylic type ester having the formula R 0 OHFl-ii-O-R' where R represents a member of the group consisting of H and CH and R is an alkyl group containing 1 to 8 carbon atoms, said heating being carried out in the presence of a free radical polymerization catalyst.

where R represents a member of the group consisting of H and CH and R is an alkyl group containing 1 to 8 carbon atoms.

6. A composition of matter comprising a volatile organic solvent solution of 5 to parts of an organic solvent soluble thermosetting arninoplast resin selected from the group consisting of urea-aldehyde resins, melaminealdehyde resins, and dicyandiamide-aldehyde resins and to 40 parts of a resin comprising the addition polymerization product of (a) 5 to 30 parts glycerol u-monoallyl ether, (b) 5 to 15 parts of an acrylic monomer of the group consisting of acrylic acid and methacrylic acid, and (c) parts of an acrylic type ester having the formula where R represents a member of the group consisting of H and CH and R is an alkyl group containing 1 to 8 carbon atoms.

OTHER REFERENCES Modern Plastics, September 1947, pages 128-129, 212

and 214. 

5. A COMPOSITION OF MATTER COMPRISING 5 TO 60 PARTS OF AN ORGANIC SOLVENT SOLUBLE THERMOSETTING AMINOPLAST RESIN SELECTED FROM THE GROUP CONSISTING OF UREA-ALDEHYDE RESINS, MELAMINE-ALDEHYDE RESINS, AND DICYANDIAMIDEALDEHYDE RESINS AND 95 TO 40 PARTS OF A RESIN COMPRISING THE ADDITION POLYMERIZATION PRODUCT OF (A) 5 TO 30 PARTS GLYCEROL A-MONO-ALLYL ETHER, (B) 5 TO 15 PARTS OF AN ACRYLIC MONOMER OF THE GROUP CONSISTING OF ACRYLIC ACID AND METHACRYLIC ACID, AND (C) 100 PARTS OF AN ACRYLIC TYPE ESTER HAVING THE FORMULA 